US20150180032A1 - Cobalt-stabilized lithium metal oxide electrodes for lithium batteries - Google Patents

Cobalt-stabilized lithium metal oxide electrodes for lithium batteries Download PDF

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US20150180032A1
US20150180032A1 US14/554,762 US201414554762A US2015180032A1 US 20150180032 A1 US20150180032 A1 US 20150180032A1 US 201414554762 A US201414554762 A US 201414554762A US 2015180032 A1 US2015180032 A1 US 2015180032A1
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layered
electrode material
spinel
lithium
metal
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Michael M. Thackeray
Jason R. CROY
Brandon R. LONG
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UChicago Argonne LLC
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C01G45/125—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO3)n-, e.g. CaMnO3
    • C01G45/1257—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO3)n-, e.g. CaMnO3 containing lithium, e.g. Li2MnO3 or Li2(MxMn1-x)O3
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/54—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (Mn2O4)-, e.g. Li(NixMn2-x)O4 or Li(MyNixMn2-x-y)O4
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • This invention relates to electrode materials for electrochemical cells and batteries. Such cells and batteries are used widely to power numerous devices, for example, portable electronic appliances and medical, transportation, aerospace, and defense systems.
  • LiMO 2 M ⁇ Mn, Co, Ni
  • spinel LiMn 2 O 4 olivine LiFePO 4
  • Approaches that are currently being adopted to enhance the energy of lithium-ion batteries include the exploitation of composite cathode structures that offer a significantly higher capacity compared to conventional cathode materials.
  • the present invention provides a three-component, ‘layered-layered-spinel’, composite lithium metal oxide electrode material, which in an initial state (i.e., as prepared) has the formula: y[xLi 2 MO 3 .(1-x)LiM′O 2 ].( 1 -y)Li 1+d Mn 2-z-d M′′ z O 4 ; wherein 0 ⁇ x ⁇ 1; 0.75 ⁇ y ⁇ 1; 0 ⁇ z ⁇ 2; 0 ⁇ d ⁇ 0.2; and z-d ⁇ 2.
  • M comprises one or more metal ions that together have a combined average oxidation state of +4 (e.g., Mn, Ti and Zr); M′ comprises one or more metal ions that together have a combined average oxidation state of +3 (e.g., Mn and Ni, or Mn, Ni and Co); and M′′ comprises one or more metal ions (e.g., Ni, Co, or Ni and Co) that together with the Mn and any excess proportion of lithium, “d”, in the spinel formula above have a combined average oxidation state between +3.5 and +4; preferably, M′′ includes at least some Co.
  • +4 e.g., Mn, Ti and Zr
  • M′ comprises one or more metal ions that together have a combined average oxidation state of +3 (e.g., Mn and Ni, or Mn, Ni and Co)
  • M′′ comprises one or more metal ions (e.g., Ni, Co, or Ni and Co) that together with the Mn and any excess proportion of lithium, “d
  • the Li 1+d Mn 2-z-d M′′ z O 4 component comprises a spinel crystal structure, each of the Li 2 MO 3 and the LiM′O 2 components comprise layered crystal structures, and at least one of M, M′, and M′′ comprises Co.
  • the ‘layered-layered-spinel’ materials of the invention surprisingly ameliorate the voltage fade problem associated conventional ‘layered-layered’ and ‘layered-spinel’ positive electrode materials in lithium battery applications.
  • M comprises at least one metal selected from the group consisting of Mn, Ti and Zr; M′ comprises at least one metal selected from the group consisting of Mn, Ni, and Co, and M′′ comprises at least one metal selected from the group consisting of Ni, and Co.
  • each of M and M′ can independently further comprise at least one metal selected from the group consisting of Al, Mg, and Li;
  • M can further comprise at least one metal selected from the group consisting of a first or second row transition metal other than Mn, Ti, and Zr;
  • M′ can further comprise at least one metal selected from the group consisting of a first or second row transition metal other than Mn, Ni and Co, provided that the average oxidation state of the combined M ions is +4, and the average oxidation state of the combined M′ ions is +3;
  • M′′ can further comprise at least one metal selected from the group consisting of Al, Mg, and a first or second row transition metal other than Ni and Co (e.g., Ti, Fe, Zr) such that the M′′ ions in the spinel formula Li 1+d Mn 2-z-d M′′ z O 4 have a combined average oxidation state between +3.5 and +4.
  • the spinel component Li 1+d Mn 2-z-d M′′ z O 4 , is a lithium-rich spinel (i.e., including an excess proportion of Li, represented by “d”, where 0 ⁇ d ⁇ 0.2).
  • the proportion, z, of M′′ is in the range of 0.2 ⁇ z ⁇ 0.6; and M′′ comprises Ni, Co, or a combination thereof.
  • M′′ can comprise at least one metal selected from the group consisting of Ni and Co; d>0; and 2-d-z>0.
  • M is Mn; M′ comprises Mn and Ni; and the spinel component,
  • Li 1+d Mn 2-z-d M′′ z O 4 comprises Mn, Ni, and Co.
  • M′′ can comprise at least one metal selected from the group consisting of Ni and Co; d>0; and 2-d-z>0.
  • the present invention also provides a layered-layered-spinel electrode material in which M′′ comprises Ni and Co; Co constitutes about 1 atom percent to about 30 atom percent of transition metals in the spinel component, Li 1+d Mn 2-z- d M′′ z O 4 ; and the combination of Mn and Ni constitutes about 70 atom percent to about 99 atom percent of the transition metals in the spinel component.
  • the combination of Mn and Ni constitutes about 80 atom percent of the transition metals in the spinel component and Co constitutes about 20 atom percent of the transition metals in the spinel component.
  • the spinel component constitutes about 50 atom percent Mn, about 30 atom percent Ni, and about 20 atom percent Co, based on the total transition metals in the spinel component.
  • composition of the layered-layered-spinel electrodes of this invention can therefore be tailored for optimum electrochemical performance.
  • cobalt content plays a significant role in determining the performance of these materials.
  • the present invention provides a positive electrode for a lithium electrochemical cell comprising ‘layered-layered-spinel’ electrode material, preferably in contact with a metal current collector. If, desired, the ‘layered-layered-spinel’ materials can be formulated with another active electrode material, such as carbon.
  • the electrode is useful as a positive electrode in lithium electrochemical cells and batteries.
  • FIG. 1 depicts a Li 2 MO 3 -LiM′O 2 -LiM′′ 2 O 4 phase diagram, in which Li 2 MO 3 , LiM′O 2 , and Li 1+d Mn 2-z-d M′′ z O 4 (represented for simplicity as LiM′′ 2 O 4 , i.e., where d is 0 and M′′ includes the Mn portion of the spinel) are the layered, layered, and spinel components of a layered-layered-spinel electrode material.
  • FIG. 2 depicts (a) the electrochemical cycling behavior and voltage fade and (b) corresponding dQ/dV plots of a ‘layered-layered’ 0.5Li 2 MnO 3 .0.5LiMn 0.5 O 2 electrode in a lithium half-cell, charged and discharged between 4.6 and 2.0 V.
  • FIG. 3 depicts (a) the electrochemical cycling behavior and (b) corresponding dQ/dV plots of a ‘layered-layered-spinel’ electrode of this invention derived from a lithium-deficient 0.25Li 2 MnO 3 .0.75LiMn 0.375 Ni 0.375 Co 0.25 O 2 composition to generate 15% spinel in the composite structure.
  • FIG. 4 depicts the X-ray diffraction patterns of (left) ‘layered-layered’ 0.25Li 2 MnO 3 .0.75LiMn 0.375 Ni 0.375 Co 0.25 O 2 products when synthesized from a metal oxalate and Li 2 MnO 3 precursors, and (right) layered-layered spinel products synthesized from lithium-deficient compositions of 0.25Li 2 MnO 3 .0.75LiMn 0.375 Ni 0.375 Co 0.25 O 2 .
  • FIG. 5 depicts (top) the electrochemical profiles of lithium half cells in which the 0.25Li 2 MnO 3 .0.75LiMn 0.375 Ni 0.375 Co 0.25 O 2 cathode was prepared from (left) oxalate and (right) Li 2 MnO 3 precursors, the cells being charged and discharged between 4.45 and 2.0 V, after an initial activation charge to 4.6 V, at 15 mA/g.
  • FIG. 6 depicts (top) the electrochemical profiles of lithium half cells in which the ‘layered-layered-spinel’ cathode with 15% spinel was derived from a 0.25Li 2 MnO 3 .0.75LiMn 0.375 Ni 0.375 Co 0.25 O 2 composition prepared from (left) oxalate and (right) Li 2 MnO 3 precursors, the cells being charged and discharged between 4.45 and 2.0 V, after an initial activation charge to 4.6 V, at 15 mA/g.
  • FIG. 7 depicts the first-cycle discharge capacity ( ⁇ ) and first-cycle efficiency ( ⁇ ) as a function of cathode composition, x, in Li x Mn 0.53125 Ni 0.28125 Co 0.18750 O 6 and the corresponding target spinel content as a percentage in the ‘layered-layered-spinel’ cathode.
  • FIG. 8 provides plots of voltage versus capacity (Panel A) and normalized capacity (Panel B) for samples of 0.5Li 2 MnO 3 .0.5LiCoO 2 prepared at temperatures ranging from 400 to 900° C.
  • FIG. 9 provides plots of first cycle charge capacity, discharge capacity, and efficiency for samples using a layered-layered template, i.e., a pristine layered-layered 0.1Li 2 MnO 3 .0.9LiMn 0.4 Ni 0.55 Co 0.05 O 2 composition, an acid-treated pristine sample with additional Co annealed at 450° C. for three hours, and an acid-treated pristine sample with additional Co annealed at 750° C. for six hours.
  • a layered-layered template i.e., a pristine layered-layered 0.1Li 2 MnO 3 .0.9LiMn 0.4 Ni 0.55 Co 0.05 O 2 composition
  • FIG. 10 provides plots of voltage versus capacity for selected acid-treated 0.1Li 2 MnO 3 .0.9LiMn 0.4 Ni 0.55 Co 0.005 O 2 materials.
  • FIG. 11 depicts a schematic representation of an electrochemical cell.
  • FIG. 12 depicts a schematic representation of a battery consisting of a plurality of cells connected electrically in series and in parallel.
  • This invention relates to cobalt-stabilized lithium-metal oxide electrodes that fall within the scope of structurally compatible, composite ‘layered-layered’ and ‘layered-spinel’ materials that contain a layered Li 2 MnO 3 component. Selected compositions of these materials have been discovered that appear to arrest a voltage fade phenomenon which occurs when state-of-the-art ‘layered-layered’ and ‘layered-spinel’ electrode materials are repeatedly cycled in lithium cells.
  • the preferred precursor compound for synthesizing the improved compounds and compositions of the invention comprises Li 2 MnO 3 (or in conventional layered notation Li[Li 1/3 Mn 2/3 ]O 2 ).
  • the voltage fade of high-capacity ‘layered-layered’ xLi 2 MnO 3 .(1-x)LiMO 2 electrodes, in which M is a metal cation is comprised, typically of Mn, Ni and Co, can be suppressed by introducing a spinel component into the ‘layered-layered’ structure by careful selection and control of the Li 2 MnO 3 and Co content and overall composition of the resulting ‘layered-layered-spinel’ products.
  • the materials of the invention can be defined on a ‘layered-layered-spinel’ Li 2 MO 3 -LiM′O 2 —LiM′′ 2 O 4 phase diagram, shown schematically in FIG.
  • Li 2 MO 3 , LiM′O 2 , and Li 1+d M′′ 2 O 4 are the layered, layered, and spinel components, respectively, that described the overall composition of the electrode within the Li 2 MO 3 -LiM′O 2 -LiM′′ 2 O 4 phase diagram; and where M is one or more metal cations with a combined average tetravalent oxidation state, preferably Mn 4+ ; M′ is one or more metal cations with a combined average trivalent oxidation state, preferably comprising manganese, nickel and cobalt ions, and M′′ comprises one or more metal cations with a combined average oxidation state of between +3.5 and +4.0, preferably comprising manganese, nickel and cobalt ions, optionally with lithium ions.
  • the composite ‘layered-layered-spinel’ electrode structures and materials of this invention (which can, in general, be regarded overall as a composite structure with both layered and spinel character), have the advantage of providing a voltage profile with both the sloping character of the layered components and the voltage plateaus of the spinel components, thus smoothing the overall voltage profile of high capacity, structurally-integrated, ‘composite’ layered-spinel electrodes of this invention.
  • the spinel electrode materials of this invention are broad in compositional scope and structure.
  • the metal cations are distributed in octahedral sites in alternating close-packed oxygen layers in a 3:1 ratio of transition metals to Li, whereas, in an ideal LiM′O 2 layered structure, the M′ transition metal cations occupy all the octahedral sites in alternating layers, without any Li being present in those layers. Therefore, in the composite layered-spinel structures of this invention, the ratio of metal cations in alternating layers of the close-packed oxygen array can vary within the structure from the 3:1 transition metal to Li ratio of an ideal spinel configuration to the corresponding ideal layered configuration with no lithium in the transition metal layers.
  • the Li, Mn, M, M′ and M′′ cations of the spinel and layered electrode materials of this invention can be partially disordered over the octahedral and tetrahedral sites of the layered and spinel components of the composite y[xLi 2 MO 3 .( 1 -x)LiM′O 2 ].( 1 -y)Li 1+d Mn 2-z-d M′′ z O 4 lithium metal oxide structure, yielding complex cation arrangements in the spinel and layered components and in the overall and highly complex ‘layered-layered-spinel’ composite structures.
  • the structural complexity of the electrodes of the invention makes it difficult to distinguish the individual components from one another, particularly when the intergrown layered Li 2 MO 3 and LiM′O 2 components are disordered within a single, structurally-compatible close-packed oxide array, in which case the electrode composition can be simply regarded as, and represented, by a ‘layered-spinel’ structure.
  • FIG. 2 panel (a) shows the electrochemical cycling behavior and voltage fade of a typical ‘layered-layered’ 0.5Li 2 MnO 3 .0.5LiMn 0.5 Ni 0.5 O 2 electrode in a lithium half-cell, when the cells are charged and discharged continuously between 4.6 and 2.0 V.
  • FIG. 3 panels (a) and (b), respectively.
  • This electrode was activated by an initial charge/discharge cycle between 4.6 and 2.0 V and then subsequently charged and discharged between 4.45 and 2.0 V.
  • the voltage profiles ( FIG. 3 , panel (a)) and corresponding dQ/dV plots ( FIG. 3 , panel (b)) indicate remarkable cycling stability relative to those in FIG.
  • the electrode compositions and structures of this invention can be synthesized by using Li 2 MnO 3 as a precursor and reacting it with the required amount of Ni and Co in solution followed by a heat-treatment step, as described by Croy et al., in Electrochemistry Communications, Volume 13, pages 1063-1066 (2011).
  • a ‘layered-layered’ product with a targeted composition 0.25Li 2 MnO 3 .0.75LiMn 0.375 Ni 0.375 Co 0.25 O 2 can be prepared by reacting a Li 2 MnO 3 precursor with the stoichiometrically-required amounts of nickel and cobalt nitrates in a 0.1 M solution of HNO 3 , and then stirring the mixture overnight at room temperature.
  • compositions of the advanced materials of this invention can be synthesized by other processing methods that are known in the art, for example, by sol-gel and precipitation processing techniques using precursors that decompose during synthesis, such as metal hydroxides, carbonates and oxalates, or by solid state reactions, thereby broadening the scope of this invention.
  • FIGS. 4 to 6 The versatility in synthesizing the ‘layered-layered-spinel’ electrode materials of this invention are demonstrated in FIGS. 4 to 6 by methods using (1) metal oxide precursors and (2) a Li 2 MnO 3 template into which the required metal cations and oxygen are introduced to create the composite structures as described by Croy et al., in Electrochemistry Communications, Volume 13, pages 1063-1066 (2011).
  • FIG. 4 shows the powder X-ray diffraction patterns (CuK ⁇ radiation) of a ‘layered-layered’ 0.25Li 2 MnO 3 .0.75LiMn 0.375 Ni 0.375 Co 0.25 O 2 composition (i.e., targeting 0% spinel in the structure) using manganese, nickel and cobalt oxalate precursors and the same composition using a Li 2 MnO 3 template for comparison;
  • FIG. 4 (right) shows the powder X-ray diffraction patterns of a ‘layered-layered-spinel product with 15% spinel derived from 0.25Li 2 MnO 3 .0.75LiMn 0.375 Ni 0.375 Co 0.25 O 2 by reducing the lithium content in the starting precursors by 9%.
  • These X-ray diffraction patterns are similar, highlighting the difficulty in differentiating the ‘layered-layered’ structures from ‘layered-layered-spinel’ derivatives by routine X-ray diffraction methods.
  • Cathodes for the electrochemical tests were prepared by coating Al foil with a slurry containing 82 percent by weight (wt %) of the oxide powder, 8 wt % SUPER P carbon (TIMCAL Ltd.), and 10 wt % polyvinylidene difluoride (PVDF) binder in NMP and assembled in coin cells (size 2032).
  • the cells contained a metallic lithium anode.
  • the electrolyte was a 1.2 M solution of LiPF 6 in a 3:7 mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC).
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • FIG. 5 shows (top, left and right) the electrochemical cycling profiles and (bottom) the corresponding dQ/dV plots of Li/0.25Li 2 MnO 3 .0.75LiMn 0.375 Ni 0.375 Co 0.25 O 2 cells, in which the cathode was synthesized by the oxalate and Li 2 MnO 3 methods, respectively, when cycled between 4.45 and 2.0 V after an initial activation charge to 4.6 V. Both cells show exceptional stability over this voltage range with insignificant voltage fade relative to the data of the ‘layered-layered’ 0.5Li 2 MnO 3 .0.75LiMn 0.5 Ni 0.5 O 2 electrode shown in FIG. 2 .
  • FIG. 6 shows (top, left and right) the electrochemical cycling profiles and (bottom) the corresponding dQ/dV plots of lithium cells in which the ‘layered-layered-spinel’ cathode, when synthesized by the oxalate and Li 2 MnO 3 methods, respectively, was derived from a 0.25Li 2 MnO 3 .0.75LiMn 0.375 Ni 0.375 Co 0.25 O 2 composition by reducing the lithium in the composition by 9%, when cycled between 4.45 and 2.0 V after an initial activation charge to 4.6 V.
  • FIG. 7 A plot of first-cycle capacity and first-cycle efficiency vs. lithium (spinel) content of a lithium cell containing the ‘Li x Mn 0.53125 Ni 0.28125 Co 0.18750 O ⁇ ’ electrode is shown in FIG. 7 .
  • the top x-axis shows the increasing target spinel content as a function of decreasing lithium content.
  • the electrodes were first charged to 4.6 V and discharged to 2.0 V in lithium coin cells.
  • the plot of solid squares indicates that the electrode capacity reaches a maximum by lowering the lithium content corresponding to spinel content of approximately 6%, after which the electrode capacity decreases, in accordance with a significant advantage of the layered-layered-spinel electrodes of this invention over conventional layered-layered electrodes.
  • the invention extends to include lithium metal oxide electrode materials (e.g., lithium-rich spinels, layered oxides, and the like) with surface modification, for example, with metal-oxide, metal-fluoride or metal-phosphate layers or coatings to protect the electrode materials from highly oxidizing potentials in the cells and from other undesirable effects, such as electrolyte oxidation, oxygen loss, and/or dissolution.
  • lithium metal oxide electrode materials e.g., lithium-rich spinels, layered oxides, and the like
  • surface modification for example, with metal-oxide, metal-fluoride or metal-phosphate layers or coatings to protect the electrode materials from highly oxidizing potentials in the cells and from other undesirable effects, such as electrolyte oxidation, oxygen loss, and/or dissolution.
  • Such surface protection enhances the surface stability, rate capability and cycling stability of the electrode materials.
  • individual particles of a powdered lithium metal oxide composition, a surface of the formed electrode, or both are coated or treated, e.g., in situ during synthesis, for example, with a metal oxide, a metal fluoride, a metal polyanionic material, or a combination thereof, e.g., at least one material selected from the group consisting of (a) lithium fluoride, (b) aluminum fluoride, (c) a lithium-metal-oxide in which the metal is selected preferably, but not exclusively, from the group consisting of Al and Zr, (d) a lithium-metal-phosphate in which the metal is selected from the group consisting preferably, but not exclusively, of Fe, Mn, Co, and Ni, and (e) a lithium-metal-silicate in which the metal is selected from the group consisting preferably, but not exclusively, of Al and Zr.
  • a metal oxide, a metal fluoride, a metal polyanionic material, or a combination thereof e.g., at least one
  • the constituents of the treatment or coating such as the aluminum and fluoride ions of an AlF 3 coating, the lithium and phosphate ions of a lithium phosphate coating, or the lithium, nickel and phosphate ions of a lithium-nickel-phosphate coating can be incorporated in a solution that is contacted with the hydrogen-lithium-manganese-oxide material or the lithium-manganese-oxide precursor when forming the electrodes of this invention.
  • the surface may be treated with fluoride ions, for example, using NH 4 F, in which case, the fluoride ions may substitute for oxygen at the surface or at least partially within the bulk of the electrode structure.
  • the data in FIG. 8 show the first cycle voltage profiles when cycled between 4.6 and 2 V at 15 mA/g for 0.5Li 2 MnO 3 .0.5LiCoO 2 compositions made at temperatures in the range of 400 to 900° C.
  • the incorporation of a “low-temperature” LiCoO 2 lithiated spinel component (i.e., Li 2 [Co 2 ]O 4 ) into a layered-layered composite structure (i.e., control of stabilizing Co in the Li layer) is evident in the 400° C. and 500° C. samples, which exhibited a 3.4 V plateau. Above these temperatures, it appears that the Co migrates into the transition metal layer to induce greater layered character to the electrode.
  • FIG. 8 , Panel B shows the normalized first cycle discharge voltage profile which clearly illustrates the presence of the 3.4 V plateau.
  • the Co can be introduced into a series of layered Ni/Mn/Co and layered-layered compositions with increasing Li content (i.e., increasing ‘layered-layered’ character).
  • the material prepared at lower synthesis temperature showed an increase in 3.4 V plateau capacity associated with stabilizing Co in the Li layer in a Ni containing oxide.
  • FIG. 10 shows the first cycle voltage profiles for the samples from FIG. 9 plus additional acid treated samples with additional (50%) Co.
  • the acid treatment process did not remove significant Li content, as evidenced by the similar discharge capacity for all samples.
  • the lower temperature samples (450° C.) exhibited a 3.4 V plateau attributed to stabilizing Co in the Li layer, whereas the higher temperature sample (750° C.) did not.
  • a significant advantage of having cobalt in the lithium layer is that it can impart the characteristic discharge voltage of a LiCo 2 O 4 spinel at 3.4 V, which can be used as an end-of-discharge indicator for the electrodes of this invention.
  • the invention can be extended to include electrodes that contain, for example, a LiNi 2 O 4 spinel component, stabilized by the layered component of the composite structure, which is believed would provide an elevated discharge voltage relative to LiMn 2 O 4 ( ⁇ 2.9 V), similar to a LiCo 2 O 4 spinel, or a material such as LiCo 2-x Ni x O 4 , LiCo 2-x-y Ni x Mn z O 4 , and the like.
  • a LiNi 2 O 4 spinel component stabilized by the layered component of the composite structure, which is believed would provide an elevated discharge voltage relative to LiMn 2 O 4 ( ⁇ 2.9 V), similar to a LiCo 2 O 4 spinel, or a material such as LiCo 2-x Ni x O 4 , LiCo 2-x-y Ni x Mn z O 4 , and the like.
  • FIG. 11 A detailed schematic illustration of a lithium electrochemical cell 10 of the invention is shown in FIG. 11 .
  • Cell 10 comprises negative electrode 12 separated from positive electrode 16 by a separator 14 saturated with the electrolyte, all contained in insulating housing 18 with suitable terminals (not shown) being provided in electronic contact with negative electrode 12 and positive electrode 16 of the invention.
  • Positive electrode 16 comprises metallic collector plate 15 and active layer 17 comprising the cobalt-stabilized lithium metal oxide material described herein.
  • FIG. 12 provides a schematic illustration of one example of a battery in which two strings of electrochemical cells 10 , described above, are arranged in parallel, each string comprising three cells 10 arranged in series.

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Abstract

A three-component, layered-layered-spinel, composite lithium metal oxide electrode material, in an initial state has the formula:
y[xLi2MO3.(1-x)LiM′O2].(1-y)Li1+dMn2-z-dM″zO4; wherein 0≦x≦1; 0.75≦y<1; 0<z≦2; 0≦d≦0.2; and z-d≦2. M comprises one or more metal ions that together have an average oxidation state of +4; M′ comprises one or more metal ions that together have an average oxidation state of +3; and M″ comprises one or more metal ions that together with the Mn and any excess proportion of lithium, “d”, have a combined average oxidation state between +3.5 and +4. The Li1+dMn2-z-dM″zO4 component comprises a spinel crystal structure, each of the Li2MO3 and the LiM′O2 components comprise layered crystal structures, and at least one of M, M′, and M″ comprises Co. Cells and batteries comprising the electrode material also are described.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application claims the benefit of U.S. Provisional Application Ser. No. 61/920,283, filed on Dec. 23, 2013, which is incorporated by reference in its entirety.
    • CONTRACTUAL ORIGIN OF THE INVENTION
  • The United States Government has rights in this invention pursuant to Contract No. DE-AC02-06CH11357 between the United States Government and UChicago Argonne, LLC representing Argonne National Laboratory.
    • FIELD OF THE INVENTION
  • This invention relates to electrode materials for electrochemical cells and batteries. Such cells and batteries are used widely to power numerous devices, for example, portable electronic appliances and medical, transportation, aerospace, and defense systems.
    • BACKGROUND
  • State-of-the-art lithium batteries do not provide sufficient energy to power electric vehicles for an acceptable driving range. This limitation arises because the electrodes, both the anode, typically graphite, and the cathode, typically, layered LiMO2 (M═Mn, Co, Ni), spinel LiMn2O4 and olivine LiFePO4, do not offer sufficient capacity or a high enough electrochemical potential to meet the energy demands. Approaches that are currently being adopted to enhance the energy of lithium-ion batteries include the exploitation of composite cathode structures that offer a significantly higher capacity compared to conventional cathode materials. In particular, lithium-rich and manganese-rich high capacity cathodes, such as xLi2MnO3.(1-x)LiMO2 (M=Mn, Ni, Co) materials (often referred to as ‘layered-layered’ materials, because both the Li2MnO3 and LiMO2 components have layered-type structures) suffer from ‘voltage fade’ on repeated cycling, which reduces the energy output and efficiency of the cell, thereby compromising the management of cell/battery operation.
  • There is an ongoing need for new electrode materials to ameliorate the problems associated with the voltage fade of ‘layered-layered’ electrode materials. The electrodes, electrochemical cells, and batteries of this invention address this need.
    • SUMMARY OF THE INVENTION
  • The present invention provides a three-component, ‘layered-layered-spinel’, composite lithium metal oxide electrode material, which in an initial state (i.e., as prepared) has the formula: y[xLi2MO3.(1-x)LiM′O2].(1-y)Li1+dMn2-z-dM″zO4; wherein 0≦x≦1; 0.75≦y<1; 0<z≦2; 0≦d≦0.2; and z-d≦2. M comprises one or more metal ions that together have a combined average oxidation state of +4 (e.g., Mn, Ti and Zr); M′ comprises one or more metal ions that together have a combined average oxidation state of +3 (e.g., Mn and Ni, or Mn, Ni and Co); and M″ comprises one or more metal ions (e.g., Ni, Co, or Ni and Co) that together with the Mn and any excess proportion of lithium, “d”, in the spinel formula above have a combined average oxidation state between +3.5 and +4; preferably, M″ includes at least some Co. The Li1+dMn2-z-d M″zO4 component comprises a spinel crystal structure, each of the Li2MO3 and the LiM′O2 components comprise layered crystal structures, and at least one of M, M′, and M″ comprises Co. In some embodiments, 0.85≦y<1 or 0.9≦y<1, or 0.85≦y≦0.9. Preferably, 0≦x≦0.5. The ‘layered-layered-spinel’ materials of the invention surprisingly ameliorate the voltage fade problem associated conventional ‘layered-layered’ and ‘layered-spinel’ positive electrode materials in lithium battery applications.
  • Preferably, M comprises at least one metal selected from the group consisting of Mn, Ti and Zr; M′ comprises at least one metal selected from the group consisting of Mn, Ni, and Co, and M″ comprises at least one metal selected from the group consisting of Ni, and Co. Optionally, each of M and M′ can independently further comprise at least one metal selected from the group consisting of Al, Mg, and Li; M can further comprise at least one metal selected from the group consisting of a first or second row transition metal other than Mn, Ti, and Zr; M′ can further comprise at least one metal selected from the group consisting of a first or second row transition metal other than Mn, Ni and Co, provided that the average oxidation state of the combined M ions is +4, and the average oxidation state of the combined M′ ions is +3; and M″ can further comprise at least one metal selected from the group consisting of Al, Mg, and a first or second row transition metal other than Ni and Co (e.g., Ti, Fe, Zr) such that the M″ ions in the spinel formula Li1+dMn2-z-d M″zO4 have a combined average oxidation state between +3.5 and +4.
  • In some embodiments, the spinel component, Li1+dMn2-z-d M″zO4, is a lithium-rich spinel (i.e., including an excess proportion of Li, represented by “d”, where 0<d≦0.2). Preferably, the proportion, z, of M″ is in the range of 0.2<z≦0.6; and M″ comprises Ni, Co, or a combination thereof. For example, M″ can comprise at least one metal selected from the group consisting of Ni and Co; d>0; and 2-d-z>0. In some other preferred embodiments, M is Mn; M′ comprises Mn and Ni; and the spinel component,
  • Li1+dMn2-z-dM″zO4, comprises Mn, Ni, and Co. For example, M″ can comprise at least one metal selected from the group consisting of Ni and Co; d>0; and 2-d-z>0.
  • The present invention also provides a layered-layered-spinel electrode material in which M″ comprises Ni and Co; Co constitutes about 1 atom percent to about 30 atom percent of transition metals in the spinel component, Li1+dMn2-z- dM″zO4; and the combination of Mn and Ni constitutes about 70 atom percent to about 99 atom percent of the transition metals in the spinel component. Preferably, the combination of Mn and Ni constitutes about 80 atom percent of the transition metals in the spinel component and Co constitutes about 20 atom percent of the transition metals in the spinel component. In a preferred embodiment, the spinel component constitutes about 50 atom percent Mn, about 30 atom percent Ni, and about 20 atom percent Co, based on the total transition metals in the spinel component.
  • The composition of the layered-layered-spinel electrodes of this invention can therefore be tailored for optimum electrochemical performance. In particular, it has been discovered that the cobalt content plays a significant role in determining the performance of these materials.
  • In another aspect, the present invention provides a positive electrode for a lithium electrochemical cell comprising ‘layered-layered-spinel’ electrode material, preferably in contact with a metal current collector. If, desired, the ‘layered-layered-spinel’ materials can be formulated with another active electrode material, such as carbon. The electrode is useful as a positive electrode in lithium electrochemical cells and batteries.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • The invention consists of certain novel features and a combination of parts hereinafter fully described, illustrated in the accompanying drawings, it being understood that various changes in the details may be made without departing from the spirit, or sacrificing any of the advantages of the present invention.
  • FIG. 1 depicts a Li2MO3-LiM′O2-LiM″2O4 phase diagram, in which Li2MO3, LiM′O2, and Li1+dMn2-z-d M″zO4 (represented for simplicity as LiM″2O4, i.e., where d is 0 and M″ includes the Mn portion of the spinel) are the layered, layered, and spinel components of a layered-layered-spinel electrode material.
  • FIG. 2 depicts (a) the electrochemical cycling behavior and voltage fade and (b) corresponding dQ/dV plots of a ‘layered-layered’ 0.5Li2MnO3.0.5LiMn0.5O2 electrode in a lithium half-cell, charged and discharged between 4.6 and 2.0 V.
  • FIG. 3 depicts (a) the electrochemical cycling behavior and (b) corresponding dQ/dV plots of a ‘layered-layered-spinel’ electrode of this invention derived from a lithium-deficient 0.25Li2MnO3.0.75LiMn0.375Ni0.375Co0.25O2 composition to generate 15% spinel in the composite structure.
  • FIG. 4 depicts the X-ray diffraction patterns of (left) ‘layered-layered’ 0.25Li2MnO3.0.75LiMn0.375Ni0.375Co0.25O2 products when synthesized from a metal oxalate and Li2MnO3 precursors, and (right) layered-layered spinel products synthesized from lithium-deficient compositions of 0.25Li2MnO3.0.75LiMn0.375Ni0.375Co0.25O2.
  • FIG. 5 depicts (top) the electrochemical profiles of lithium half cells in which the 0.25Li2MnO3.0.75LiMn0.375Ni0.375Co0.25O2 cathode was prepared from (left) oxalate and (right) Li2MnO3 precursors, the cells being charged and discharged between 4.45 and 2.0 V, after an initial activation charge to 4.6 V, at 15 mA/g.
  • FIG. 6 depicts (top) the electrochemical profiles of lithium half cells in which the ‘layered-layered-spinel’ cathode with 15% spinel was derived from a 0.25Li2MnO3.0.75LiMn0.375Ni0.375Co0.25O2 composition prepared from (left) oxalate and (right) Li2MnO3 precursors, the cells being charged and discharged between 4.45 and 2.0 V, after an initial activation charge to 4.6 V, at 15 mA/g.
  • FIG. 7 depicts the first-cycle discharge capacity (▪) and first-cycle efficiency (□) as a function of cathode composition, x, in LixMn0.53125Ni0.28125Co0.18750O6 and the corresponding target spinel content as a percentage in the ‘layered-layered-spinel’ cathode.
  • FIG. 8 provides plots of voltage versus capacity (Panel A) and normalized capacity (Panel B) for samples of 0.5Li2MnO3.0.5LiCoO2 prepared at temperatures ranging from 400 to 900° C.
  • FIG. 9 provides plots of first cycle charge capacity, discharge capacity, and efficiency for samples using a layered-layered template, i.e., a pristine layered-layered 0.1Li2MnO3.0.9LiMn0.4Ni0.55Co0.05O2 composition, an acid-treated pristine sample with additional Co annealed at 450° C. for three hours, and an acid-treated pristine sample with additional Co annealed at 750° C. for six hours.
  • FIG. 10 provides plots of voltage versus capacity for selected acid-treated 0.1Li2MnO3.0.9LiMn0.4Ni0.55Co0.005O2 materials.
  • FIG. 11 depicts a schematic representation of an electrochemical cell.
  • FIG. 12 depicts a schematic representation of a battery consisting of a plurality of cells connected electrically in series and in parallel.
    •  DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
  • This invention relates to cobalt-stabilized lithium-metal oxide electrodes that fall within the scope of structurally compatible, composite ‘layered-layered’ and ‘layered-spinel’ materials that contain a layered Li2MnO3 component. Selected compositions of these materials have been discovered that appear to arrest a voltage fade phenomenon which occurs when state-of-the-art ‘layered-layered’ and ‘layered-spinel’ electrode materials are repeatedly cycled in lithium cells. The preferred precursor compound for synthesizing the improved compounds and compositions of the invention comprises Li2MnO3 (or in conventional layered notation Li[Li1/3Mn2/3]O2).
  • Broadly speaking, it has been discovered that the voltage fade of high-capacity ‘layered-layered’ xLi2MnO3.(1-x)LiMO2 electrodes, in which M is a metal cation is comprised, typically of Mn, Ni and Co, can be suppressed by introducing a spinel component into the ‘layered-layered’ structure by careful selection and control of the Li2MnO3 and Co content and overall composition of the resulting ‘layered-layered-spinel’ products. In a general embodiment, the materials of the invention can be defined on a ‘layered-layered-spinel’ Li2MO3-LiM′O2—LiM″2O4 phase diagram, shown schematically in FIG. 1, in which Li2MO3, LiM′O2, and Li1+dM″2O4 (represented in the diagram as LiM″2O4, for simplicity, i.e., where d is 0 and M″ includes the Mn portion of the spinel) are the layered, layered, and spinel components, respectively, that described the overall composition of the electrode within the Li2MO3-LiM′O2-LiM″2O4 phase diagram; and where M is one or more metal cations with a combined average tetravalent oxidation state, preferably Mn4+; M′ is one or more metal cations with a combined average trivalent oxidation state, preferably comprising manganese, nickel and cobalt ions, and M″ comprises one or more metal cations with a combined average oxidation state of between +3.5 and +4.0, preferably comprising manganese, nickel and cobalt ions, optionally with lithium ions. For example, the average oxidation state of a Li1+dMn2-z-dM″zO4 component in which d=0 and z=0 would be +3.5, whereas for d=0.333 and z=0 (i.e., Li1.333Mn1.667O4), it would be +4.0.
  • The composite ‘layered-layered-spinel’ electrode structures and materials of this invention (which can, in general, be regarded overall as a composite structure with both layered and spinel character), have the advantage of providing a voltage profile with both the sloping character of the layered components and the voltage plateaus of the spinel components, thus smoothing the overall voltage profile of high capacity, structurally-integrated, ‘composite’ layered-spinel electrodes of this invention. The spinel electrode materials of this invention are broad in compositional scope and structure. In an ideal LiM″2O4 spinel structure, the metal cations are distributed in octahedral sites in alternating close-packed oxygen layers in a 3:1 ratio of transition metals to Li, whereas, in an ideal LiM′O2 layered structure, the M′ transition metal cations occupy all the octahedral sites in alternating layers, without any Li being present in those layers. Therefore, in the composite layered-spinel structures of this invention, the ratio of metal cations in alternating layers of the close-packed oxygen array can vary within the structure from the 3:1 transition metal to Li ratio of an ideal spinel configuration to the corresponding ideal layered configuration with no lithium in the transition metal layers. Furthermore, the Li, Mn, M, M′ and M″ cations of the spinel and layered electrode materials of this invention can be partially disordered over the octahedral and tetrahedral sites of the layered and spinel components of the composite y[xLi2MO3.(1-x)LiM′O2].(1-y)Li1+dMn2-z-d M″zO4 lithium metal oxide structure, yielding complex cation arrangements in the spinel and layered components and in the overall and highly complex ‘layered-layered-spinel’ composite structures. In some instances, the structural complexity of the electrodes of the invention makes it difficult to distinguish the individual components from one another, particularly when the intergrown layered Li2MO3 and LiM′O2 components are disordered within a single, structurally-compatible close-packed oxide array, in which case the electrode composition can be simply regarded as, and represented, by a ‘layered-spinel’ structure.
  • The principles of the invention are embodied in FIG. 2 and FIG. 3. FIG. 2, panel (a), shows the electrochemical cycling behavior and voltage fade of a typical ‘layered-layered’ 0.5Li2MnO3.0.5LiMn0.5Ni0.5O2 electrode in a lithium half-cell, when the cells are charged and discharged continuously between 4.6 and 2.0 V. FIG. 2, panel (b), shows the corresponding dQ/dV plots of the data in panel (a). These data clearly highlight the electrochemical and concomitant structural decay of the xLi2MnO3.(1-x)LiMO2 electrode that leads to energy loss and inefficiency of the lithium cell on repeated cycling.
  • The electrochemical and corresponding dQ/dV plots of an advanced ‘layered-layered-spinel’ electrode of this invention derived from a lithium-deficient 0.25Li2MnO3.0.75 LiMn0.375Ni0.375Co0.25O2 precursor to generate 15% spinel in the composite structure are shown in FIG. 3, panels (a) and (b), respectively. This electrode was activated by an initial charge/discharge cycle between 4.6 and 2.0 V and then subsequently charged and discharged between 4.45 and 2.0 V. The voltage profiles (FIG. 3, panel (a)) and corresponding dQ/dV plots (FIG. 3, panel (b)) indicate remarkable cycling stability relative to those in FIG. 2 without any significant redox process occurring below 3.5 V, while still generating between 180 and 200 mAh/g for twenty cycles. This surprisingly improved performance is attributed to the spinel component within the composite structure, notably cobalt-rich spinel components, LiM2O4, in which M is predominantly Co and Ni relative to Mn and Li. In this respect, it is to be noted that a Li[Co2]O4 spinel is known to accommodate lithium at approximately 3.4 V, which emphasizes the advantage of using a cobalt or cobalt-substituted Li[Co2-xMx]O4 spinel to stabilize the cycling performance of ‘layered-layered’ electrodes.
  • The electrode compositions and structures of this invention can be synthesized by using Li2MnO3 as a precursor and reacting it with the required amount of Ni and Co in solution followed by a heat-treatment step, as described by Croy et al., in Electrochemistry Communications, Volume 13, pages 1063-1066 (2011). For example, a ‘layered-layered’ product with a targeted composition 0.25Li2MnO3.0.75LiMn0.375Ni0.375Co0.25O2 can be prepared by reacting a Li2MnO3 precursor with the stoichiometrically-required amounts of nickel and cobalt nitrates in a 0.1 M solution of HNO3, and then stirring the mixture overnight at room temperature. Thereafter, the liquid from the solution is evaporated at approximately 70° C., and the resulting solid product collected and ground to a powder. The powder is then annealed at about 850° C. for about 24 hours in air. Variations in synthesis parameters, e.g., temperature, dwell times, rates of cooling, etc., can be used to optimize the structures and electrochemical properties of the materials of this invention for a given application or use. In order to synthesize ‘layered-layered-spinel’ products of this invention, the same procedure is followed, as described above, but using a smaller amount of lithium than is required for the ‘layered-layered’ composition, which drives the composition of the final product toward the LiM″2O4 spinel apex of the phase diagram in FIG. 1, thereby resulting in the ‘layered-layered-spinel’ products. Alternatively, the compositions of the advanced materials of this invention can be synthesized by other processing methods that are known in the art, for example, by sol-gel and precipitation processing techniques using precursors that decompose during synthesis, such as metal hydroxides, carbonates and oxalates, or by solid state reactions, thereby broadening the scope of this invention.
  • Specific examples of the processing methods that were employed to synthesize the electrodes of this invention are:
    • 1. (NiMnCo)C2O4 (i.e., metal oxalate) precursors were prepared from NiSO4.6H2O, MnSO4.H2O, CoSO4.7H2O, and Na2C2O4 using the required ratios of Ni, Mn and Co for a targeted stoichiometry in the final product (the ‘oxalate method’). An aqueous solution containing the required stoichiometric amounts of metal sulfates was added under stirring into a solution of sodium oxalate. The solution was then stirred for about 3 hours at about 70° C. The co-precipitated powder was filtered, washed, and dried in air at about 105° C. The dried powders were thoroughly mixed with stoichiometric amounts of lithium carbonate and annealed at about 450° C. for about 12 hours in air, followed by grinding and an annealing step at about 750° C. for about 12 hours (also in air) to prepare materials with a desired composition. Other annealing conditions included no intermediate firing step, different annealing times and different temperatures.
    • 2. Materials from Li2MnO3 precursors were prepared by the following procedure: Li2MnO3 was added under stirring into a 0.1 M HNO3 solution at room temperature (the ‘Li2MnO3 method’). The required amounts of Ni(NO3)2.6H2O, Co(NO3)2.6H2O, and LiNO3 for a desired stoichiometry in the final product were added to the solution and subsequently stirred overnight. The solution was then heated to dryness at approximately 80° C., then the solid product was ground and annealed in air at about 850° C. for about 24 hours.
  • The versatility in synthesizing the ‘layered-layered-spinel’ electrode materials of this invention are demonstrated in FIGS. 4 to 6 by methods using (1) metal oxide precursors and (2) a Li2MnO3 template into which the required metal cations and oxygen are introduced to create the composite structures as described by Croy et al., in Electrochemistry Communications, Volume 13, pages 1063-1066 (2011).
  • For example, FIG. 4 (left) shows the powder X-ray diffraction patterns (CuKα radiation) of a ‘layered-layered’ 0.25Li2MnO3.0.75LiMn0.375Ni0.375Co0.25O2 composition (i.e., targeting 0% spinel in the structure) using manganese, nickel and cobalt oxalate precursors and the same composition using a Li2MnO3 template for comparison; FIG. 4 (right) shows the powder X-ray diffraction patterns of a ‘layered-layered-spinel product with 15% spinel derived from 0.25Li2MnO3.0.75LiMn0.375Ni0.375Co0.25O2 by reducing the lithium content in the starting precursors by 9%. These X-ray diffraction patterns are similar, highlighting the difficulty in differentiating the ‘layered-layered’ structures from ‘layered-layered-spinel’ derivatives by routine X-ray diffraction methods.
  • Cathodes for the electrochemical tests were prepared by coating Al foil with a slurry containing 82 percent by weight (wt %) of the oxide powder, 8 wt % SUPER P carbon (TIMCAL Ltd.), and 10 wt % polyvinylidene difluoride (PVDF) binder in NMP and assembled in coin cells (size 2032). The cells contained a metallic lithium anode. The electrolyte was a 1.2 M solution of LiPF6 in a 3:7 mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC). Coin cells were assembled in a glovebox under an inert argon atmosphere.
  • FIG. 5 shows (top, left and right) the electrochemical cycling profiles and (bottom) the corresponding dQ/dV plots of Li/0.25Li2MnO3.0.75LiMn0.375Ni0.375Co0.25O2 cells, in which the cathode was synthesized by the oxalate and Li2MnO3 methods, respectively, when cycled between 4.45 and 2.0 V after an initial activation charge to 4.6 V. Both cells show exceptional stability over this voltage range with insignificant voltage fade relative to the data of the ‘layered-layered’ 0.5Li2MnO3.0.75LiMn0.5Ni0.5O2 electrode shown in FIG. 2.
  • FIG. 6 shows (top, left and right) the electrochemical cycling profiles and (bottom) the corresponding dQ/dV plots of lithium cells in which the ‘layered-layered-spinel’ cathode, when synthesized by the oxalate and Li2MnO3 methods, respectively, was derived from a 0.25Li2MnO3.0.75LiMn0.375Ni0.375Co0.25O2 composition by reducing the lithium in the composition by 9%, when cycled between 4.45 and 2.0 V after an initial activation charge to 4.6 V. Both cells cycled with exceptional stability over this voltage range, delivering a steady capacity between 180 and 190 mAh/g at an average voltage of approximately 3.54 V with insignificant voltage fade relative to the data of the ‘layered-layered’ 0.5Li2MnO3.0.5LiMn0.5LiMn0.5Ni0.5O2 electrode shown in FIG. 2.
  • A series of ‘layered-layered-spinel’ electrode compositions with varying spinel content, synthesized by the ‘oxalate method’, was investigated electrochemically. For one experiment, electrodes were prepared by using less lithium than would normally be used for synthesizing a layered-layered' electrode of nominal composition 0.25Li2MnO3.0.75LiMn0.375Ni0.375Co0.250O2 in which the Mn:Ni:Co ratio is 0.53125:0.28125:0.18750; this ‘layered-layered-spinel’ electrode is normalized to read ‘LixMn0.53125Ni0.28125Co0.18750Oδ’ for convenience and simplicity, with the value of x=1.25 and δ=2.25 representing the parent ‘layered-layered’ composition 0.25Li2MnO3.0.75LiMn0.375Ni0.375Co0.250O2 . A plot of first-cycle capacity and first-cycle efficiency vs. lithium (spinel) content of a lithium cell containing the ‘LixMn0.53125Ni0.28125Co0.18750Oδ’ electrode is shown in FIG. 7. The top x-axis shows the increasing target spinel content as a function of decreasing lithium content. The electrodes were first charged to 4.6 V and discharged to 2.0 V in lithium coin cells. The plot of solid squares indicates that the electrode capacity reaches a maximum by lowering the lithium content corresponding to spinel content of approximately 6%, after which the electrode capacity decreases, in accordance with a significant advantage of the layered-layered-spinel electrodes of this invention over conventional layered-layered electrodes. Lowering the lithium content, thereby increasing the spinel content, also has the significant advantage of increasing the first-cycle efficiency of the cell (open squares). The invention extends to include lithium metal oxide electrode materials (e.g., lithium-rich spinels, layered oxides, and the like) with surface modification, for example, with metal-oxide, metal-fluoride or metal-phosphate layers or coatings to protect the electrode materials from highly oxidizing potentials in the cells and from other undesirable effects, such as electrolyte oxidation, oxygen loss, and/or dissolution. Such surface protection enhances the surface stability, rate capability and cycling stability of the electrode materials.
  • In some embodiments, individual particles of a powdered lithium metal oxide composition, a surface of the formed electrode, or both, are coated or treated, e.g., in situ during synthesis, for example, with a metal oxide, a metal fluoride, a metal polyanionic material, or a combination thereof, e.g., at least one material selected from the group consisting of (a) lithium fluoride, (b) aluminum fluoride, (c) a lithium-metal-oxide in which the metal is selected preferably, but not exclusively, from the group consisting of Al and Zr, (d) a lithium-metal-phosphate in which the metal is selected from the group consisting preferably, but not exclusively, of Fe, Mn, Co, and Ni, and (e) a lithium-metal-silicate in which the metal is selected from the group consisting preferably, but not exclusively, of Al and Zr. In a preferred embodiment of the invention, the constituents of the treatment or coating, such as the aluminum and fluoride ions of an AlF3 coating, the lithium and phosphate ions of a lithium phosphate coating, or the lithium, nickel and phosphate ions of a lithium-nickel-phosphate coating can be incorporated in a solution that is contacted with the hydrogen-lithium-manganese-oxide material or the lithium-manganese-oxide precursor when forming the electrodes of this invention. Alternatively, the surface may be treated with fluoride ions, for example, using NH4F, in which case, the fluoride ions may substitute for oxygen at the surface or at least partially within the bulk of the electrode structure.
  • Preferably, a formed positive electrode comprises at least about 50 percent by weight (wt %) of a powdered lithium metal oxide composition comprising the lithium-rich spinel material, and an electrochemically inert polymeric binder (e.g., polyvinylidene difluoride; PVDF). Optionally, the positive electrode can comprise up to about 40 wt % carbon (e.g., carbon back, graphite, carbon nanotubes, carbon microspheres, carbon nanospheres, or any other form of particulate carbon).
  • In another example, the data in FIG. 8, Panel A, show the first cycle voltage profiles when cycled between 4.6 and 2 V at 15 mA/g for 0.5Li2MnO3.0.5LiCoO2 compositions made at temperatures in the range of 400 to 900° C. The incorporation of a “low-temperature” LiCoO2 lithiated spinel component (i.e., Li2[Co2]O4) into a layered-layered composite structure (i.e., control of stabilizing Co in the Li layer) is evident in the 400° C. and 500° C. samples, which exhibited a 3.4 V plateau. Above these temperatures, it appears that the Co migrates into the transition metal layer to induce greater layered character to the electrode. FIG. 8, Panel B, shows the normalized first cycle discharge voltage profile which clearly illustrates the presence of the 3.4 V plateau.
  • In another embodiment, the Co can be introduced into a series of layered Ni/Mn/Co and layered-layered compositions with increasing Li content (i.e., increasing ‘layered-layered’ character). The material prepared at lower synthesis temperature showed an increase in 3.4 V plateau capacity associated with stabilizing Co in the Li layer in a Ni containing oxide.
  • The compositions and structures of this invention can be synthesized by various processing methods, such as acid treatment of a layered, two-component, layered-layered material, or a three-component, layered-layered-spinel template or precursor as described by Croy et. al., in Electrochemistry Communications, Volume 13, pages 1063-1066 (2011). For example, FIG. 9 shows the first cycle charge capacity, discharge capacity, and efficiency for samples using a layered-layered template: (1) a pristine layered-layered 0.1Li2MnO3.0.9LiMn0.4Ni0.55Co0.05O2 composition, (2) an acid treated pristine sample with additional Co annealed at 450° C. for three hours, and (3) an acid treated pristine sample with additional Co annealed at 750° C. for six hours. All three samples deliver approximately 200 to 205 mAh/g first cycle discharge capacity when cycled between 4.6 and 2 V at 15 mA/g. The addition of stabilizing Co at low temperatures improved the first cycle efficiency without sacrificing discharge capacity.
  • FIG. 10 shows the first cycle voltage profiles for the samples from FIG. 9 plus additional acid treated samples with additional (50%) Co. The acid treatment process did not remove significant Li content, as evidenced by the similar discharge capacity for all samples. The lower temperature samples (450° C.) exhibited a 3.4 V plateau attributed to stabilizing Co in the Li layer, whereas the higher temperature sample (750° C.) did not. A significant advantage of having cobalt in the lithium layer is that it can impart the characteristic discharge voltage of a LiCo2O4 spinel at 3.4 V, which can be used as an end-of-discharge indicator for the electrodes of this invention. By analogy, the invention can be extended to include electrodes that contain, for example, a LiNi2O4 spinel component, stabilized by the layered component of the composite structure, which is believed would provide an elevated discharge voltage relative to LiMn2O4 (˜2.9 V), similar to a LiCo2O4 spinel, or a material such as LiCo2-xNixO4, LiCo2-x-yNix MnzO4, and the like.
    • Exemplary Electrochemical Cell and Battery.
  • A detailed schematic illustration of a lithium electrochemical cell 10 of the invention is shown in FIG. 11. Cell 10 comprises negative electrode 12 separated from positive electrode 16 by a separator 14 saturated with the electrolyte, all contained in insulating housing 18 with suitable terminals (not shown) being provided in electronic contact with negative electrode 12 and positive electrode 16 of the invention. Positive electrode 16 comprises metallic collector plate 15 and active layer 17 comprising the cobalt-stabilized lithium metal oxide material described herein. FIG. 12 provides a schematic illustration of one example of a battery in which two strings of electrochemical cells 10, described above, are arranged in parallel, each string comprising three cells 10 arranged in series.
  • All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
  • The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. The terms “consisting of” and “consists of” are to be construed as closed terms, which limit any compositions or methods to the specified components or steps, respectively, that are listed in a given claim or portion of the specification. In addition, and because of its open nature, the term “comprising” broadly encompasses compositions and methods that “consist essentially of” or “consist of” specified components or steps, in addition to compositions and methods that include other components or steps beyond those listed in the given claim or portion of the specification. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All numerical values obtained by measurement (e.g., weight, concentration, physical dimensions, removal rates, flow rates, and the like) are not to be construed as absolutely precise numbers, and should be considered to encompass values within the known limits of the measurement techniques commonly used in the art, regardless of whether or not the term “about” is explicitly stated. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate certain aspects of the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
  • Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

Claims (21)

1. A three-component, layered-layered-spinel composite lithium metal oxide electrode material, which in an initial state has the formula:

y[xLi2MO3.(1-x)LiM′O2].(1-y)Li1+dMn2-z-dM″zO4;
wherein:
0≦x≦1;
0.75≦y<1;
0≦z≦2;
0≦d≦0.2;
z-d≦2;
M comprises one or more metal ions that together have a combined average oxidation state of +4;
M′ comprises one or more metal ions that together have a combined average oxidation state of +3; and
M″ comprises one or more metal ions that together with the Mn and excess proportion, d, of lithium, have a combined average oxidation state of +3.5; and
wherein the LiM″O4 component comprises a spinel crystal lattice structure, each of the Li2MO3 and the LiM″O2 components thereof comprise layered crystal lattice structures; and at least one of M, M′, and M″ comprises Co.
2. The electrode material of claim 1, wherein 0.85≦y<1.
3. The electrode material of claim 1, wherein 0.9≦y<1.
4. The electrode material of claim 1, wherein 0.85≦y≦0.9.
5. The electrode material of claim 1, wherein each of M and M′ independently comprises at least one metal selected from the group consisting of Mn, Ni, and Co; and M″ comprises at least one metal selected from the group consisting of Ni and Co.
6. The electrode material of claim 5, wherein each of M and M′ independently further comprises at least one metal selected from the group consisting of Al, Mg, Li, and a first or second row transition metal other than Mn, Ni and Co; and M″ further comprises at least one metal selected from the group consisting of Al, Mg, and a first or second row transition metal other than Mn, Ni and Co.
7. The electrode material of claim 1, wherein 0<d≦0.2; 0.2<z≦0.6; and M″ comprises Ni, Co, or a combination thereof.
8. The electrode material of claim 1, wherein M is Mn.
9. The electrode material of claim 1, wherein M′ comprises Mn and Ni.
10. The electrode material of claim 9, wherein M′ further comprises Co.
11. The electrode material of claim 1, wherein the spinel component, Li1+dMn2-z-dM″zO4, comprises Mn, Ni, and Co.
12. The electrode material of claim 1, wherein M is Mn; M′ comprises Mn and Ni; and the spinel component, Li1+dMn2-z-dM″zO4 comprises Mn, Ni, and Co.
13. The electrode material of claim 1, wherein M″ comprises at least one metal selected from the group consisting of Ni and Co; d>0; and 2-d-z>0.
14. The electrode material of claim 1, wherein M″ comprises Ni and Co; Co constitutes about 1 atom percent to about 30 atom percent of transition metals in spinel component, Li1+dMn2-z-dM″zO4; and the combination of Mn and Ni constitutes about 70 atom percent to about 99 atom percent of the transition metals in the spinel component.
15. The electrode material of claim 14, wherein the combination of Mn and Ni constitutes about 80 atom percent of the transition metals in the spinel component and Co constitutes about 20 atom percent of the transition metals in the spinel component.
16. The electrode material of claim 14, wherein the spinel component constitutes about 50 atom percent Mn, about 30 atom percent Ni, and about 20 atom percent Co of the transition metals in the spinel component.
17. The electrode material of claim 1, wherein the Li, Mn, M, M′ and M″ cations are partially disordered over the octahedral and tetrahedral sites of the layered and spinel components of the composite lithium metal oxide structure.
18. The electrode material of claim 1, wherein 0≦x≦0.5.
19. A positive electrode for a lithium electrochemical cell comprising a layer of the electrode material of claim 1 in contact with a metal current collector.
20. A lithium electrochemical cell comprising the positive electrode of claim 19 and a negative electrode in contact with a non-aqueous electrolyte comprising a lithium salt.
21. A lithium battery comprising a plurality of the electrochemical cells of claim 20 connected together in series, parallel, or both.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170047587A1 (en) * 2015-08-11 2017-02-16 Uchicago Argonne, Llc Stabilized electrodes for lithium batteries
EP3163656A1 (en) * 2015-10-28 2017-05-03 Samsung Electronics Co., Ltd. Composite positive electrode active material, positive electrode including the same, and lithium battery including the positive electrode
US10044030B2 (en) * 2014-07-18 2018-08-07 Samsung Electronics Co., Ltd. Composite positive electrode active material positive electrode including the same, and lithium battery including the positive electrode
US10862106B2 (en) 2015-10-28 2020-12-08 Samsung Electronics Co., Ltd. Composite positive electrode active material, positive electrode including the same, and lithium battery including the positive electrode
EP4261950A4 (en) * 2022-02-21 2024-12-18 Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences Cobalt-free layered oxide positive electrode material
US12206101B2 (en) 2017-06-02 2025-01-21 Uchicago Argonne, Llc Disordered rock salt electrodes for lithium batteries

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040076882A1 (en) * 2002-01-08 2004-04-22 Yosuke Hosoya Positive plate active material and nonaqyeous electrolyte secondary cell using same
JP2008084743A (en) * 2006-09-28 2008-04-10 Nec Tokin Corp Positive electrode for secondary battery and secondary battery using the same
KR20100044651A (en) * 2008-10-22 2010-04-30 (주)텔레콤랜드 Triple band metro optic repeater system and its signal transmisson method
KR20120139449A (en) * 2011-06-17 2012-12-27 주식회사 엘지화학 Mn-based cathode material of high capacity and lithium secondary battery containing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040076882A1 (en) * 2002-01-08 2004-04-22 Yosuke Hosoya Positive plate active material and nonaqyeous electrolyte secondary cell using same
JP2008084743A (en) * 2006-09-28 2008-04-10 Nec Tokin Corp Positive electrode for secondary battery and secondary battery using the same
KR20100044651A (en) * 2008-10-22 2010-04-30 (주)텔레콤랜드 Triple band metro optic repeater system and its signal transmisson method
KR20120139449A (en) * 2011-06-17 2012-12-27 주식회사 엘지화학 Mn-based cathode material of high capacity and lithium secondary battery containing the same

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
machine translation of JP 2008-084743, retrieved from <https://www.j-platpat.inpit.go.jp/web/all/top/BTmTopEnglishPage> on 7/13/2016. *
machine translation of KR 1020100044651, retrieved from <http://kposd.kipo.go.kr:8088/up/kpion/> on 7/15/2016. *
machine translation of KR 1020120139449, retrieved from <http://kposd.kipo.go.kr:8088/up/kpion/> on 7/15/2016. *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10044030B2 (en) * 2014-07-18 2018-08-07 Samsung Electronics Co., Ltd. Composite positive electrode active material positive electrode including the same, and lithium battery including the positive electrode
US20170047587A1 (en) * 2015-08-11 2017-02-16 Uchicago Argonne, Llc Stabilized electrodes for lithium batteries
US10305103B2 (en) * 2015-08-11 2019-05-28 Uchicago Argonne, Llc Stabilized electrodes for lithium batteries
EP3163656A1 (en) * 2015-10-28 2017-05-03 Samsung Electronics Co., Ltd. Composite positive electrode active material, positive electrode including the same, and lithium battery including the positive electrode
KR20170049424A (en) * 2015-10-28 2017-05-10 삼성전자주식회사 Composite positive active material, positive electrode including the same, and lithium battery including the positive electrode
CN106953070A (en) * 2015-10-28 2017-07-14 三星电子株式会社 Composite cathode active material including its positive pole and the lithium battery including positive pole
US10862106B2 (en) 2015-10-28 2020-12-08 Samsung Electronics Co., Ltd. Composite positive electrode active material, positive electrode including the same, and lithium battery including the positive electrode
US11764352B2 (en) 2015-10-28 2023-09-19 Samsung Electronics Co., Ltd. Composite positive electrode active material, positive electrode including the same, and lithium battery including the positive electrode
KR102701080B1 (en) * 2015-10-28 2024-09-02 삼성전자주식회사 Composite positive active material, positive electrode including the same, and lithium battery including the positive electrode
US12206101B2 (en) 2017-06-02 2025-01-21 Uchicago Argonne, Llc Disordered rock salt electrodes for lithium batteries
EP4261950A4 (en) * 2022-02-21 2024-12-18 Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences Cobalt-free layered oxide positive electrode material

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